JPH05125295A - Coating resin composition with excellent thermal resistance - Google Patents

Abstract

PURPOSE:To obtain the title composition which is so excellent in thermal resistance, flexibility and electrical properties that it is suitable for use in a thermally stable coating agent or paint in the field of electrical and electronic components. CONSTITUTION:The title composition comprises polyparabanic acid optionally modified at its end groups, a polymerizable unsaturated compound having a vinyl group and free radical initiator.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating resin composition having good heat resistance, which can be cured by heat and is excellent in heat resistance, flexibility and electrical characteristics.
The present invention relates to a resin composition that can be suitably used for various applications such as paints and inks.

[0002]

2. Description of the Related Art In recent years, in the field of electric and electronic parts, there is an increasing demand for miniaturization and high performance of component mounting. The coating agents and paints used therefor have heat resistance and adhesion. Further improvements in various characteristics such as electrical characteristics are required. Conventionally, it has been required to have excellent heat resistance, adhesiveness, electrical characteristics, etc., for example, for heat resistant coating agents and paints typified by cover coating agents for flexible printed circuit boards. ,
Epoxy resins, phenol resins, melamine resins, aminoalkyd resins and the like are used, but these have insufficient heat resistance and electrical characteristics, and are unable to satisfy the required performance.

Recently, super engineering plastics such as polyimide, polyamide-imide, polyester sulfone, and polyparabanic acid have been highlighted as those having higher heat resistance and electrical characteristics than the above-mentioned conventional resins. A coating agent and a paint using is developed.

However, although polyimide-based coating agents and the like are excellent in heat resistance and electric characteristics, they are
It entails problems such as high temperatures of 250 to 350 ° C. and high solution viscosity, making it difficult to obtain high solids concentrations, and thus the thickness of the resulting coating film becomes thicker. is doing.

[0006]

SUMMARY OF THE INVENTION In view of the above technical background, the present invention has a performance satisfying the above-mentioned requirements, can solve the problems in work, and has a good heat resistance. It is intended to provide a composition.

[0007]

Means for Solving the Problems The present invention comprises a terminal-modified polyparabanic acid having a terminal modified with a modifier or a polyunsaturated compound having a double bond and a radical polymerization initiator, or The present invention relates to a coating resin composition having good heat resistance, which comprises terminal-modified polyparabanic acid whose terminals are modified with a modifier or a polymer of a polymerizable unsaturated compound having the above double bond.

The polyparabanic acid resin (hereinafter referred to as PPA) used in the present invention contains the repeating unit represented by the general formula of the following chemical formula 1, preferably 75% or more of which is the general chemical formula of the following chemical formula 2. It is a polymer containing a repeating unit represented by the formula.

[Chemical 1]

[Chemical 2][In the formulas 1 and 2, Z¹And Z²Is an oxygen atom
Ku NH group (provided that Z¹ And Z² Are not NH groups at the same time)
And R is a group exemplified in the following Chemical formulas 3 to 7,

[Chemical 3]

[Chemical 4]

[Chemical 5]

[Chemical 6]

[Chemical 7] R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms or methyl groups, X ¹ and X ² are bonds,
CH ₂ -, an oxygen atom, a sulfur atom, -SO ₂ -, - CO-
Alternatively, it represents a group represented by the following chemical formula 8. ]

[Chemical 8] Polymers comprising repeating units of the above formula 1 are known, and are produced, for example, by reacting a diisocyanate compound represented by the general formula OCN-R-NCO (where R is as defined above) with hydrogen cyanide. can do.
The manufacturing method thereof is disclosed in, for example, US Pat. No. 3,661,859. Further, PPA composed of the repeating unit represented by the chemical formula 2 is obtained by hydrolyzing a polymer composed of the repeating unit represented by the chemical formula 1. The method is
For example, the above-mentioned U.S. patent specification, JP-A-58-179230.
As described in Japanese Patent Application Laid-Open Publication No. H11-242242, a polymer composed of repeating units of the chemical formula 1 is prepared by adding an aqueous solution of Bronsted acid such as hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, or the presence of anhydrous hydrogen chloride or anhydrous hydrogen bromide. It may be hydrolyzed below. The degree of hydrolysis can be adjusted by appropriately selecting the hydrolysis conditions such as the concentration of Bronsted acid and the like, the use ratio thereof, the temperature, the time, etc., and PPA having a repeating unit of the chemical formula 2 of 75% or more is obtained. be able to. As a specific example of the diisocyanate compound represented by the above general formula, which is used when producing a polymer comprising a repeating unit of the chemical formula 1, m is
-Phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p
-Phenylene diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-biphenyl diisocyanate
, Trizine diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl thioether diisocyanate, 4,4 ' -Diphenyl sulfone diisocyanate, 4,4'-benzophenone diisocyanate, 4,4'-diphenylisopropylidene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, etc. Be done. These diisocyanate compounds can be used alone or in combination of two or more kinds. Further, other diisocyanate compounds can be used as long as the properties of the obtained polymer are not impaired. Specific examples of other diisocyanate compounds that can be used in the present invention include m-xylylene diisocyanate, p-xylylene diisocyanate, 3,
3'-dimethoxy-4,4'-biphenylene diisocyanate, 4- (4-isocyanate cyclohexyl) phenyl isocyanate, 4-isocyanate benzyl isocyanate, tetrafluoro-p-phenylene 3,4'-diisocyanate octafluoro-biphenyl and duren diisocyanate;
3'-Dimethyl-4,4'-methylenebis (cyclohexyl isocyanate), 1,4-diisocyanate cyclohexane and isophorone diisocyanate; hexamethylene diisocyanate, dodecamethylene diisocyanate And an alkylene group such as 2,2,4-trimethylhexamethylene diisocyanate, an arylene group, a cycloalkylene group and a diisocyanate compound having a group derived therefrom as a main chain, and an alkyl group Examples thereof include diisocyanate compounds having an aliphatic hydrocarbon group in the main chain such as di- (3-isocyanatopropyl) ether bonded by a valent group or atom. The PPA used in the present invention has an intrinsic viscosity (0.
5 g / 100 ml-dimethylformamide, 30 ° C.) is 0.1-1.5, preferably 0.2-
It is preferably in the range of 1.3 deciliters / gram. In the present invention, polyparabanic acid having its terminal modified with a modifying agent can be used. Examples of the modifier include allyl group-containing compounds such as carboxylic acid anhydride, allyl alcohol, allylamine, and allyl isocyanate, cinnamic alcohol, hydroxyethyl methacrylate, hydroxyethyl acrylate, and the like. (Meth) acrylates may be mentioned. Specific examples of the carboxylic acid anhydride include:
Formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid,
Acid anhydrides of aliphatic monocarboxylic acids such as caproic acid, pivalic acid, acrylic acid, methacrylic acid and crotonic acid; of aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid and maleic acid Acid anhydrides; Acid anhydrides of oxycarboxylic acids such as tartaric acid;
Acid anhydrides of alicyclic carboxylic acids such as cyclohexane monocarboxylic acid, cyclohexene monocarboxylic acid, cis-1,2-cyclohexanedicarboxylic acid, cis-4-methylcyclohexene-1,2-dicarboxylic acid; benzoic acid,
Acid anhydrides of aromatic monocarboxylic acids such as toluic acid, anisic acid, p-tertiary butyl benzoic acid, naphthoic acid and cinnamic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalic acid, trimellitic acid, hemimellitic acid , Tolmesic acid, pyromellitic acid, and acid anhydrides of polyvalent aromatic carboxylic acids such as mellitic acid. These acid anhydrides can be used alone or in combination. The polyparabanic acid whose terminal has been modified with a modifier can be obtained by allowing the modifier to coexist in the reaction system when producing PPA. The terminal modified P
By using PA, the solubility of PPA in the polymerizable unsaturated compound having a double bond can be increased, and the softening temperature of the composition can be increased.

[0009] polymerizable unsaturated compound having a double bond used in the present invention is an ethylenically unsaturated compound having a -CH = CH ₂ groups having the property of polymerizing by a radical polymerization initiator described later, preferably Is the following compound. (1) Polymerizable unsaturated compound having an amide group or an acyclic amino group in the molecule. Specific examples thereof include N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-vinylpyrrolidone, N, N. -Dimethylaminopropyl methacrylamide, diacetone methacrylamide, N, N-dimethylaminoethyl methacrylate, methylol acrylamide, N-butoxymethyl acrylamide, t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate Rate can be cited. (2) Glycidyl group-containing vinyl monomers Specific examples thereof include glycidyl acrylate and glycidyl methacrylate. Among these, particularly, N-N-dimethylacrylamide, which can dissolve the terminal-modified PPA or PPA, N,
N-dimethylmethacrylamide, N-vinylpyrrolidone, glycidyl acrylate, glycidyl methacrylate
Etc. are preferred. In addition, styrene compounds such as styrene and vinyltoluene, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate It is also possible to use an alkyl ester of acrylic acid such as rate, n-hexyl methacrylate, and a hydroxyl group-containing methacrylic acid derivative such as hydroxyethyl methacrylate and hydroxypropyl methacrylate.

The radical polymerization initiator used in the present invention is for radically polymerizing the polymerizable unsaturated compound having the above double bond, and is an azo compound such as azobisisobutyronitrile or an organic peroxide. Can be used, but it is preferable to use an organic peroxide. Specific examples of the organic peroxide include benzoylperoxide, t-butylhydroperoxide, di-t-butylperoxide and cumenehydroperoxide.

In the present invention, when a resin composition containing a terminal-modified PPA or a polymerizable unsaturated compound having a double bond with PPA and a radical polymerization initiator,
The compounding ratio of the terminal-modified PPA or PPA and the polymerizable unsaturated compound having a double bond is 20 to 60% by weight (wt)% in the former, preferably 30 to 50% by weight, and 40 to 80 in the latter.
wt%, preferably 50 to 70 wt%. The latter is 40 wt%
When the former is more than 60 wt% and the thermosetting property is insufficient and the curing time is long, on the other hand, when the latter is more than 80 wt% and the former is less than 20 wt%, the heat resistance is insufficient and both of It becomes difficult to achieve the purpose. The blending amount of the radical polymerization initiator is preferably 0.2 to 10 wt% with respect to the polymerizable unsaturated compound having a double bond. Below 0.2 wt%,
If the thermosetting property is insufficient, on the other hand, if it exceeds 10 wt%, the solvent resistance is lowered and the cost is increased.

Further, in the present invention, a polymer obtained by polymerizing a polymerizable unsaturated compound having a double bond with a radical polymerization initiator in advance, and a terminal-modified PPA or PPA are used.
And is blended to obtain a composition. The composition ratio is the same as the compounding ratio when the terminal-modified PPA or PPA and the polymerizable unsaturated compound are compounded.

An organic solvent may be added to the composition of the present invention for the purpose of improving coatability and printability in coating applications such as coating agents, paints and printing inks. Specific examples of the organic solvent include N-methyl-2-pyrrolidone (NM
P), dimethylformamide (DMF), dimethylacetamide, dimethylsulfoxide, cyclohexanone,
γ-butyrolactone and the like can be mentioned, and a mixed solvent may be appropriately used.

Other components may be added to the composition of the present invention, if desired. Other additives include inorganic fillers such as silica powder, titanium oxide powder and alumina powder, organic polymers such as NBR, polybutadiene, epoxy resin, colorants such as pigments, silane coupling agents or titanium coupling agents. Coupling agents and the like can be used.

[0015]

EXAMPLES The present invention will be described below based on examples.
The test method in the following examples is as follows. Measurement of softening temperature ; thermo-mechanical analyzer (TMA manufactured by Rigaku Denki Co., Ltd.)
(CN8098DI) was used as a tensile mode at a load of 2 g and a heating rate of 5 ° C./min. Example 1. N, N-dimethylacrylamide (DMA)
60 parts by weight of 4,4 'as a diisocyanate compound
-PPA synthesized using diphenylmethane diisocyanate (hereinafter referred to as PPA-M. Intrinsic viscosity: ηinh = 0.
4) 40 parts by weight of t-butyl hydroperoxide 1.5
A varnish was prepared by dissolving parts by weight. The obtained varnish was cast on an aluminum plate and heated in an oven at 100 ° C. for 5 minutes for curing to form a coating film of 35 μm.
The softening temperature of the obtained coating film was measured by the above method. Example 2. A coating film was formed in the same manner as in Example 1 except that the terminal allyl-modified PPA-M (ηinh = 0.4) modified with allyl isocyanate was used as PPA, and the softening temperature was measured. Example 3. Except that the curing conditions were 60 ° C. and 30 minutes,
A coating film was formed in the same manner as in Example 2 and the softening temperature was measured. Example 4. A coating film was formed in the same manner as in Example 2 except that di-t-butylperoxide was used as the polymerization initiator, and the softening temperature was measured. Example 5. A varnish was prepared by dissolving 30 parts by weight of the allyl-terminated PPA-M (ηinh = 0.4) used in Example 2 and 1.75 parts by weight of t-butylhydroperoxide used in 70 parts by weight of DMA to prepare a varnish. A coating film was formed and its softening temperature was measured. Example 6 60 parts by weight of N-vinylpyrrolidone (NVP) was added to 40 parts by weight of the terminal allyl-modified PPA-M used in Example 2 and t-.
1.5 parts by weight of butyl hydroperoxide was dissolved to prepare a varnish, a coating film was formed in the same manner as in Example 1, and the softening temperature thereof was measured. However, the curing condition at the time of forming the coating film was 100 ° C. for 30 minutes. Comparative Example 1. T-butyl hydroper was added to 100 parts by weight of DMA.
A mixture obtained by adding 2.5 parts by weight of oxide was heated in an oven at 100 ° C. for 60 minutes to obtain a cured product. Since the softening temperature of the obtained cured product could not be measured in the same manner as in the example, a thermomechanical analyzer (TMA manufactured by Seiko Electronics Co., Ltd.) was used.
100) in a needle insertion mode and a load of 1 g and a temperature rising rate of 10 ° C./min. Comparative example 2. To 100 parts by weight of NVP, t-butyl hydroper
A mixture obtained by adding 2.5 parts by weight of oxide was heated in an oven at 100 ° C. for 60 minutes, and the softening temperature of the cured product obtained in the same manner as in Comparative Example 1 was measured. The above results are shown in Table 1. Example 7. The polyparabanic acid used in Example 1 (P
PA-M), polyparabanic acid (PPA-TM) (η) synthesized by using an equimolar mixture of tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate as a diisocyanate compound. = 0.6), a coating film was formed in the same manner as in Example 1 and the softening temperature was measured. Example 8. A coating film was formed in the same manner as in Example 1 except that allyl-modified PPA-TM (ηinh = 0.4) obtained by modifying PPA-TM with allyl diisocyanate was used as PPA. Then, the softening temperature was measured. Example 9. A varnish was prepared in the same manner as in Example 6 except that the terminal allyl-modified PPA-TM (ηinh = 0.4) used in Example 8 was used as PPA, and then a coating film was formed in the same manner as in Example 1. Then, the softening temperature was measured. Example 10. After 233 parts by weight of N-methyl-2-pyrrolidone was added to 60 parts by weight of polydimethylacrylamide and dissolved, 40 parts by weight of PPA-M (ηinh = 0.4) was added and dissolved to prepare a varnish. The obtained varnish was cast on an aluminum plate and heated in an oven at 180 ° C. for 30 minutes to form a coating film having a thickness of 35 μm. The softening temperature was measured in the same manner as in Example 1. Example 11. A varnish was prepared in the same manner as in Example 10 except that polyvinylpyrrolidone was used instead of polydimethylacrylamide, a coating film was formed, and the softening temperature was measured. Example 12. PPA-T used in Example 7 as PPA
After adjusting the varnish in the same manner as in Example 10 except that M was used, a coating film was formed and the softening temperature thereof was measured. Example 13. PPA-T used in Example 7 as PPA
After adjusting the varnish in the same manner as in Example 11 except that M was used, a coating film was formed and the softening temperature thereof was measured.

Table 2 shows the above measurement results.

[Table 1]

[Table 2]

[0017]

Since the resin composition of the present invention has a high solid content, it is easy to obtain a thick film and is excellent in curability. INDUSTRIAL APPLICABILITY The resin composition of the present invention is excellent in heat resistance, flexibility, and electric characteristics, and therefore has excellent heat resistance in the field of electric and electronic parts.
It is possible to provide a thermosetting resin composition which is extremely useful for applications for coating agents and paints.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tadao Ikeda 109, Oji-shi, Omiya-shi, Saitama Prefectural office 32 (72) Inventor Jun Hosoda 1-28 B-702 Mudame, Kanazawa-ku, Yokohama-shi, Kanagawa

Claims (2)

[Claims] 1. A terminal-modified polyparabanic acid whose terminal is modified with a modifier, or a polymerizable unsaturated compound having a double bond and a radical polymerization initiator, or a terminal whose terminal is modified with a modifier. A coating resin composition having a good heat resistance, which comprises a modified polyparabanic acid or a polymer of a polymerizable unsaturated compound having the above double bond. 2. The polymerizable unsaturated compound having a double bond,
The coating resin composition having good heat resistance according to claim 1, which is the terminal-modified polyparabanic acid according to claim 1 or a compound capable of substantially dissolving the polyparabanic acid.